Dry cleaning detergent composition



United States Patent DRY CLEANING DETERGENT COMPOSITION Edward A. Knaggs, Deerfield, Marvin L. Nussbaum,

Skokie, and Elias Fischer, Wilmette, lll., assignors to Stepan Chemical Company, Northfield, Ill., a corporation of Delaware No Drawing. Filed Apr. 12, 1965, Ser. No. 447,514 US. Cl. 252-153 2 Claims Int. Cl. Clld 1/37; D061 1/02 ABSTRACT OF THE DISCLOSURE An improved dry cleaning composition and method of using the same by relatively unskilled workers in public coin-operated machines comprising an emulsion of water in a volatile dry cleaning solvent with a small amount of dry cleaning assistant which is a detergent component tolerant to relatively large amounts of water therein. The detergent component (y) is generally classifiable as a neutralized sulfated alkoxylated fatty alcohol which is usable per se in the dry cleaning composition or may be combined with certain minor proportions of (a) neutralized alpha-sulfo fatty ester or amide and/or with (x) sulfated alkyl chalcophenol polyalkoxide condensates.

This invention relates to improvements in dry cleaning, and more particularly, to improved compositions and methods for the dry cleaning of textile fabrics, and related fibrous materials.

It is well known that certain materials, particularly textile fabrics and similar fibrous materials, cannot usually be cleaned by means of ordinary soap and Water for the reason that they tend to shrink, fade, and/or otherwise develop undesirable characteristics when they are wetted substantially with Water. It is also known that the dry cleaning process has been developed for the purpose of cleaning such materials. In the dry cleaning process, a suitable volatile organic solvent such as Stoddards solvent, trichlorethylene, perchlorethylene, naphtha or the like known volatile organic solvents are used and these solvents are applied to the textile fabric or other material to be dry cleaned by a process hereinafter referred to generically as rinsing, but which generally involves recirculation or flowing of a stream of the solvent through a retainer or basket containing the material to be dry cleaned for a suflicient period of time to effect the desired cleaning thereof. Such solvents are effective in removing from the fabrics or other materials many grease or similar organic stains as well as dust and dirt which would ordinarily adhere to such grease stains. It is also known that it is preferable to disperse small amounts of Water in the dry cleaning fluid or solvent, and this water is believed to carry out an additional function of assisting in the cleansing and removal of water-soluble stains such as those caused by sugary liquids, etc.

Although it is known that it is usually preferable to incorporate a small amount of water (ordinarily in emulsified form in the solvent) into the dry cleaning composition, the problems of controlling this amount of water so that it may suitably carry out its own function and will not simultaneously effect undesirable results have been complicated in recent times by the use of conventional coin operated dry cleaning units by the public generally. Although the commercial dry cleaner is quite skilled in his art and ordinarily operates with various process controls so that he may maintain a desired water or moisture concentration in his dry cleaning fluid, the present dry cleaning compositions still leave much to be desired in versatility of use even by the skilled commercial operator. Onthe other hand, the members of the public using 3,433,745 Patented Mar. 18, 1969 coin operated dry cleaning devices make little or no effort to control the moisture content in the dry cleaning fluid, the relative proportions of fabric to be cleaned in quantity of dry cleaning fluid, the relative proportions of dirt to be removed and quantity of dry cleaning fluid, or even the rinsing or cleansing time in the device. This indiscriminate use of dry cleaning fluids in publicly available coin operated dry cleaning units has resulted in a number of disappointments in the dry cleaning results obtained and has made necessary the development of much more versatile dry cleaning compositions than those heretofore available.

The instant invention provides a much more versatile dry cleaning composition, primarily by virtue of the selection of the detergent or dry cleaning assistant that is added thereto in small detersive quantities. Such use of certain detergents is known and is suggested in such prior art disclosures as Flett US. Patent No. 2,326,772 and others. The instant invention involves the use of novel dry cleaning compositions containing certain selected detergets which have been found to impart unusual versatility, detersive or cleansing effect, moisture tolerance, and the like desirable properties.

It is therefore an important object of the instant invention to provide an improved dry cleaning composition and method.

In addition to the objects of providing better detersive efficiency, better water tolerance, more versatility and other superior properties in a dry cleaning composition (as well as other aspects and advantages of the invention which will be set forth hereinafter), the instant invention consists in a dry cleaning composition comprising an emulsion of water in a volatile organic'dry cleaning solvent and, as a dry cleaning assistant in a small detersive amount, a detergent component comprising (y) detergent having the formula:

wherein AO is the residue of a fatty alcohol: AOH wherein A has from six to twenty-two carbon atoms, m is an integer from 1 to 50 and M" is selected from the group consisting of alkali metals, alkaline earth metals, ammonium, (C -C alkylol) ammonium, (C -C alkoxy) (C -C alkylol) ammonium wherein n is an integer from 1 to 50, poly(C -C alkylene) amines, primary, secondary, tertiary and quaternary alkyl ammonium wherein the alkyl groups contain a total of one to twenty carbon atoms, C to C aliphatic (C -C alkylol) amines, C to C alkyl --NH-)CH amines wherein m is an integer from 1 to 4 and imidazolines having the formula:

N CH2 B -l (5H.

wherein R' is a C to C fatty acid residue and R" is selected from the group consisting of C to C alkyl, C to C alkylol and H. The instant invention further consists in the provision of a dry cleaning method using the composition set forth herein.

One of the essential ingredients used in the practice of the instant invention is a detergent hereinafter referred to as ingredient (y). Ingredient (y) is a detergent having the formula:

wherein AO' is the residue of a fatty alcohol: AOH wherein A has from six to twenty-two carbon atoms, In is an integer from 1 to 50 and M is selected from the group consisting of alkali metals, alkaline earth metals,

ammonium, (C -C alkylol) ammonium, (C -C alkoxy) (C -C alkylol) ammonium wherein n is an integer from 1 to 50, poly(C -C alkylene) amines, primary, secondary, tertiary and quaternary alkyl ammonium wherein the alkyl groups contain a total of one to twenty carbon atoms, C to C aliphatic (C -C alkylol) amines, C to C alkyl NH(CH amines wherein m is an integer from 1 to 4 and imidazolines having the formula:

NCH2

wherein R is a C to C fatty acid residue and R is selected from the group consisting of C to C alkyl, C to C alkylol and H.

Ingredient (y) is derived essentially from the fatty alcohol A-OII wherein the radical A has from 6 to 22 carbon atoms. Such fatty alcohols are available commercially as hexanol, heptanol, octanol, nonanol, decanol, dodecanol (lauryl), tetradecanol, octadecanol (stearyl and, also, oleyl alcohols), cosanol, and docosanol. In the preparation of ingredient (y), the fatty alcohol is first alkoxylated with from 1 to 50 mols of a C -C alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide. The alkoxylated compound is then sulfated, also in conventional manner; and finally the sulfated compound is neutralized to obtain the radical M.

The radical M may be an alkali metal (sodium and potassium being preferred, but lithium, etc. also being usable), ammonium, or alkaline earth (or other suitable neutralizing metallic ion from Group II of the Periodic Table, which includes magnesium, calcium, zinc, strontium, barium, etc.). In addition, the sulfated alkoxylated alcohol may be neutralized with a mono-, dior tri- (C C alkylol) amine. Such amines include monoethanol amine, diisopropanol amine, butanol amine, triethanol amine, etc.

Also, the aforementioned alkylol amines may be alkoxylfated before or after neutralization to form the radical M". These radicals are alkoxylated with from 1 to 50 mols of a suitable C -C alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide. The alkoxylation procedure is conventional.

In the practice of the instant invention, the alkyl amines have been found to be particularly useful in the formation of the radical M". Such amines as isopropyl amine and isooctyl amine have been found to be particularly useful, but primary, secondary, tertiary and quaternary alkyl amines may be used, including quaternary methyl amine, trimethyl amine, diethyl amine, lauryl amine, stearyl amine, oleyl amine, and similar amines wherein the alkyl group or groups contain a total of 1 to 20 carbon atoms.

Other amines which may be used to form the radical M" include the C -C aliphatic (C -C alkylol) amines, such as oleyl diethanolamine, and the alkyl substituted alkylene diamines, i.e., the C C alkyl-imino-alkyleneamines (e.g. Duomeen) wherein the alkylene group has from 1 to 4 methylene groups. A typical compound of this group is stearyl propylene diamine.

Still another amine which may be used to form the radical M is an imidazoline. In particular, the amines of this type which may be used in the practice of the instant invention are imidazolines having the formula:

we RIII O CH2 wherein R is a C to C fatty acid residue and R"" is selected from the group consisting of C to C alkyl, C to C alkylol and H. These imidazolines are well known and commercially available. The radical R' is preferably a C C alkyl or alkenol group, and the radical R" is preferably hydrogen, ethanol, or a stearyl group.

Although ingredient (y) may be used alone in the practice of the instant invention, as the detersive dry cleaning assistant, it is often advantageously used in combination with certain other ingredients. Another ingredient useful in the practice of the invention in this respect is herein referred to as ingredient (a). Ingredient (a) is a detergent having the formula:

R-CH-Y-X SOsM wherein Y is selected from the class consisting of and CNH

R is a C to C fatty acid residue; X is selected from the group consisting of C to C hydrocarbon, glyceryl, C C alkyl ether of glycerol, (C C alkoxyl) R wherein n is an integer from 1 to 50 and R is selected from the group consisting of H and C -C alkyl groups; and M is selected from the group consisting of alkali metals, alkaline earth metals, ammonium, (C C alkylol) ammonium, (C -C alkoxy) (C C alkylol) ammonium wherein n is an integer from 1 to 50, poly(C -C alkylene) amines, and, primary, secondary, tertiary and quaterary alkyl ammonium wherein the alkyl groups contain a total of two to twenty carbon atoms, C to C aliphatic (C2-C4 amines, C10 to C20 amines wherein m is an integer from 1 to 4 and imidazolines having the formula:

wherein R' is a C to C fatty acid residue and R"" is selected from the group consisting of C to C alkyl, C to C alkylol and H; the minimum total number of carbon atoms in any C to C chain in X plus any C to C chain in M, plus the carbon chain in R being twelve.

Ingredient (a) is a neutralized alpha-sulfo fatty ester or amide having the formula:

In general, ingredient (a) is prepared by the alpha-sulfonation of a fatty acid base having the general formula:

wherein R is a C -C fatty acid residue. The fatty acid base material (I) is preferably an ester at the time it is sulfonated, although it can be alpha-sulfonated as the acid per se (I). The radical R in the acid (I) is a typical C -C fatty acid residue, i.e. it is a fatty acid residue containing from 4 to 20 carbon atoms, so that the fatty acid base (I) is that of a C -C3 fatty acid. Such fatty acids include hexanoic (caproic), heptanoic (enanthylic), octanoic (caprylic), nonanoic (pelargonic), decanoic (capric), undecanoic (hendecanoic), (lauric), tridecanoic; tetradecanoic (myristic), pentadecanoic, hexadecanoic (palmitric), heptadecanoic (margaric), octadecanoic (stearic), nonadecanoic, eicosanic (arachidic), heneicosanic; and docosanic (behenci) acids. The acids preferred in this use are palmitic and stearic, which makes the radical R preferably a C C radical (i.e. tetradecyl to hexadecyl radical). The sulfo group replaces one of the hydrogens on the alpha carbon in the fatty acid base material (I) just described and this alpha-sulfonation may be carried out by sulfonating the fatty acid per se (in a SOsM It will be seen from the foregoing that one may start with a suitable natural oil or fat that is a triglyceride of one of the foregoing fatty acids, which fatty acids are preferably saturated by an initial hydrogenation procedure, and then by transesterification replace the glyceryl group by a methyl group so as to obtain the methyl fatty acid ester (III). This is next sulfonated with S0 to obtain the alpha-sulfonic acid of the methyl ester (IV). This general procedure is preferred for use in the prac tice of the instant invention, for the reason that the methyl ester (III) is easily produced with economic advantage of producing the by-product glycerol; and the sulfonation of the methyl ester (III) with S0 is carried out without the necessity for any additional solvents or other complications so as to obtain the alpha-sulfonic acid (IV).

Next, in the preparation of the ester compounds of the type employed in the practice of the instant invention, one may carry out additional transesterification, if desired, to replace the methyl group with another ester group X, which will be defined in further detail hereinafter, and neutralize the alpha-sulfo group with M, which will also be defined hereinafter. In contrast, if it is desired to prepare an amide for use in the practice of the instant invention, the initial alpha-sulfonated methyl ester (IV) is preferably converted to an alpha-sulfo fatty acid (VII), which in turn is converted to the amide (VIII) and neutralized to obtain the amide (IX) used in the practice of the invention.

The neutralization of the alpha-sulfonic acid group is a conventional procedure for neutralizing sulfonic groups 1n detergent materials, which involves merely reaction with a suitably alkaline material to obtain the -SO M group, wherein M is an alkali metal (sodium and potassium being preferred, but lithium, etc. also being usable), ammonium, or alkaline earth (or any suitable neutralizing metallic ion from Group II of the Periodic Table, which includes magnesium, calcium, zinc, strontium, barium, etc.). In addition, the alpha-sulfonic acid group may be neutralized with a C -C alkylol amine, so as to obtain the corresponding C -C alkylol ammonium radical, wherein there may be one to three ethanol, propanol and/ or butanol radicals attached to the ammonium N. Such radicals include monoethanol, diethanol, triethanol, monopropanol, dipropanol, etc., monobutanol, etc., ammonium radicals. In addition, the foregoing alkylol ammonium compounds may be reacted with C -C alkylene Oxides to obtain alkoxylated compounds, wherein the radical M will be a (C -C alkoxy) C -C alkylol ammonium group, wherein n is an integer from 1 to about 50. This group is prepared by conventional alkoxylation of the corresponding alkylol ammonium group, and it is possible to modify the hydrophobic-hydrophilic characteristics of the molecule by such ethoxylation procedure, although in the practice of the instant invention it is generally preferable to carry out such alkoxylation with approximately from 1 to about 50 mols of the alkylene oxide per mol of the alphasulfo compound. The alkylene oxide thus used is preferably ethylene oxide, although propylene or butylene oxide may be used in the practice of the instant invention; or mixtures thereof may be used.

It will also be appreciated that the radical M may be a primary, secondary, tertiary or quaternary alkyl am monium radical, wherein the alkyl groups contain a total of 2 to 20 carbon atoms. Such alkyl radicals may range from ethyl, isopropyl, isobutyl, etc. up to C alkyl groups. The alkyl ammonium radical may be quaternary methyl ammonium, tertiary methyl ammonium, etc., but preferably this radical M used in the practice of the instant invention is a primary alkyl ammonium group such as isopropyl ammonium or isooctyl ammonium radical.

In addition the radical M may be derived from poly(C C alkylene) amines, such as ethylene diamine, diethylene triamine, triethylene tetrarnine, etc., propylene diamine, butylene diamine, etc. In general, the polyamines contain ethylene, propylene or butylene carbon-to-carbon chains between amine groups, in a single diamine, or in repeating units in a polyalkylene polyamine compound.

The radical M may also be a C -C aliphatic amine, wherein the aliphatic group is an alkyl or alkenyl group derived from a typical fatty acid. A commercially available amine of this type which has been found to be particularly useful in the practice of the instant invention is oleyl diethanol amine. I

The radical M may also be derived from polyamines such as the commercially available Duomeen compounds. The polyamines of this type are C o-C20 m amines wherein m is an integer from 1 to 4. A typical amine of this class is stearyl propylene diamine The radical M may also be derived from the imidazolines having the formula:

wherein R is a C to C fatty acid residue and R"" is selected from the group consisting of C to C alkyl, C to C alkylol and H. In the compounds of the invention the imidazoline used preferably has a C15-C17 fatty alkyl group for the radical R', and hydrogen or an ethanol group for the radical R". The imidazolines are well known per se and these compounds are commercially available.

The ingredient (a) has, as previously indicated, the general formula:

R--CIIY-X $03M wherein Y is selected from the class consisting of II o and The compound is thus an alpha-sulfo fatty acid ester or amide. The radical X may be a C C group in that it may be methyl (which is preferred for use in the practice of the instant invention and which is also preferred for use in transesterification to obtain compound (III) from the starting material (II) hereinafter referred to). The radical X may also be ethyl, propyl, isopropyl, butyl, see-butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cosanyl, docosanyl, etc. and in each case the preferred procedure involves transesterification with the methyl compound using the corresponding ethyl, propyl, butyl, etc. alcohol to obtain the desired radical in the position X.

The radical X may also be a glyceryl or glyceryl ether radical. Again, the methyl radical in the X position can be replaced by the glyceryl or glyceryl ether group (i.e. -CH CH(OH)CH OH or CH CH (OH) CH O C -C alkyl) groups), wherein the C -C alkyl group just mentioned may be any of the typical alkyl groups such as methyl, ethyl, propyl, etc. up to hexyl. This may be done, in for example, the compound (V) merely by transesterification, or in the compound (IX) either by replacement of an alkyl group or replacement of a hydrogen on the amide group (by conventional synthesis).

In addition, the group X may be selected from groups wherein n is an integer from 1 to 50. It will be appreciated that the methyl ester (III) may be converted to a corresponding ethylene glycol ester of the general Formula V merely by a propylene or butylene glycol ester (V). Any such C C alkylene glycol ester may then be used as such in the practice of the invention or it may be alkoxylated with from 1 to 50 mols of ethylene oxide, propylene oxide and/or butylene oxide. Again, the alkoxylation process is conventional per se. Such a compound might thus be referred to as the sodium alpha-sulfate ethylene glycol stearate ester, ethoxylated with 6 mols of ethylene oxide. In addition, the ethoxylated compound may be etherified with a C to C alkyl group, such as the methyl through hexyl group hereinbefore described.

In the practice of the instant invention it has been found that there is a certain relationship concerning the total number of carbon atoms in various chains in the molecule of ingredient (a). For example, it has been found that the preferable minimum total number of carbon atoms in any carbon-to-carbon chain in X plus any carhon-to-carbon chain in M, plus the carbon chain in R should be twelve. In other words, in the computation of this total number of carbon atoms, if the radical X is an ethanol group that has been ethoxylated with 20 mols of ethylene oxide, the total number of carbon atoms in any carbonto-carbon chain in the radical X is only two. If this radical had been reacted with propylene oxide, then the total number of carbon atoms in any chain would be only three. If, for example, the M radical were isopropyl ammonium, this radical would contain a total of three carbon atoms in the chain, so that in the last mentioned situation the total number of carbon atoms in such chains in the radicals X and M would be only six. This would require a minimum of six more carbon atoms in the alkyl group R, to make a total of twelve.

Still another detergent which may be used in the practice of the instant invention is referred to herein as ingredient (x). Ingredient (x) is a detergent having the formula:

wherein R is a C to C alkyl group, 1' is an integer from one to two, n is an integer from one to fifty, D is selected from the group consisting of O and S; and M is selected from amine bases consisting of C to C aliphatic mono-, di-, triand quaternary amines, C to C aliphatic (C C alkylol) amines wherein m. is an integer from 1 to 4 and imidazolines having the formula:

NCH

I a/II! wherein R is a C to C fatty acid residue and R is selected from the group consisting of C to C alkyl, C to C alkylol and H.

Ingredient (x) is a sulfated alkyl chalcophenol polyalkoxide condensate wherein there are one to two (I -C alkyl groups attached to the benzene nucleus. Such alkyl groups may be hexyl, heptyl, octyl, nonyl, decyl, or dodecyl, and preferably the groups are octyl or nonyl, as in octyl phenol, nonyl thiophenol, octyl thiophenol, nonyl phenol and dinonyl phenol. These basic phenol materials are used as starting materials for the preparation of detergent (x). The phenol base just referred to is alkoxylated with from 1 to 50 mols of an appropriate C C alkylene oxide. In general, the total number of alkylene oxide units in the molecule is less if ethylene oxide is used alone (usually in a range of from 1 to 20 mols), but if propylene oxide is used alone or in combination with ethylene oxide, as many as 15 mols total alkoxide units may be employed. The resulting alkoxylated material is then sulfated by conventional sulfation, and then neutralized by certain selected amines or amine bases to give the radical M. The radical M may be derived from C -C aliphatic mono-, di-, triand quaternary amines. The radical M may also be derived from C -C aliphatic (C C alkylol) amines which are also available commercially. Typical amines which may be useful in the practice of the instant invention are oleyl diethanol amine, oleyl amine, lauryl amine, palymityl amine, stearyl amine, etc. Preferably the aliphatic radical in these amines is an alkyl or an alkenyl radical from a typical fatty acid source.

Another amine which may be used to obtain the radical M is a typical commercially available C -C alkyl dialkylene amine. In the alkylene group there is preferably 1 to 4 ethylene groups. A typical commercially available compound (i.e. Duomecn) is stearyl propylene diamine.

Still another amine which may be used to obtain the radical M is ingredient (x) is an imidazoline having the formula:

wherein R' is a C to C fatty acid residue and R is selected from the group consisting of C to C alkyl, C to C alkylol and H. Such imidazolines are well known compounds and are commerically available.

In the practice of the instant invention the total amount of detergent used may range from a minimum effective amount of about 0.25 to a maximum effective amount of about based on the weight of the total composition. The terms percent and parts as used herein refer to percent and parts by weight, unless otherwise designated. Preferably, the total amount of detergent used in the practice of the instant invention is within the range of 1% to 2%.

As previously indicated, the ingredient (y) may be used as the sole detersive agent in the practice of the instant invention, but it may also be used in combination with ingredients (:1) and (x). In such case, the weight ratio of ingredient (y) to the combination of ingredients (x) and (a) may range from about 34:66 to 100:1, but the amount of ingredient (y) should in any case be greater than the amount of ingredients (a) and (x). If ingredient (y) is used only in combination with ingredient (x) the weight ratio should be within the range of 51:49 to 100:1. if ingredient (y) is used only in combination with ingredient (a), the weight ratio should be within the range of about 51:49 to about 100:1.

Examples of the instant invention include dry cleaning compositions formed of perchlorethylene containing 0.1% by weight of water (emulsified therein) and 1% by weight of each of the following detergent formulations:

(y) Sulfated glycol tetradecyl ether neutralized with sodium.

(y) Sulfated lauryl alcohol (ethoxylated with 6 mols of ethylene oxide) neutralized with ethanol amine.

(y) Alkoxylated lauryl alcohol (6 mols 50:50 ethylene and propylene oxide) basic calcium sulfate.

(y) Ethoxylated stearyl alcohol mols of ethylene oxide) sulfate neutralized with stearoyl imidazoline.

(y) Ethoxylated palmityl alcohol (10 mols of ethylene oxide) sulfate neutralized with octadecyl propylene diamine.

(A) 75% of (y) sulfated glycol tetradecyl ether neutralized with sodium and 25% of sodium salt of myristamide alpha-sulfonic acid.

(B) 75% of (y) sulfated glycol tetradecyl ether neutralized with sodium and 25% of (x) sulfated nonylphenol (ethoxylated with 3 mols of ethylene oxide) neutralized with lauryl amine.

(C) 80% of (y) sulfated lauryl alcohol (ethoxylated with 6 mols of ethylene oxide) neutralized with ethanolamine, 10% of (x) sulfated nonylthiophenol (ethoxylated with 6 mols of 50:50 ethylene oxide and propylene oxide) neutralized with stearoyl imidazoline and 10% of (a) ethylenediamine (neutralized) salt of methylmyristate alphasulfonic acid.

(D) 80% of (y) alkoxylated lauryl alcohol (6 mols of 50:50 ethylene and propylene oxide) basic calcium sulfate, 10% of (x) sulfated nonylphenol (ethoxylated with 6 mols of ethylene oxide) neutralized with trimethylamine and 10% of (a) palmityl imidazoline salt of methylmyristate alpha-sulfonic acid.

(E) 75 of (y) ethoxylated stearyl alcohol (10 mols of ethylene oxide) sulfate neutralized with stearoyl imidazoline and 25% of (a) tetradecyl propylene diamine (basic) salt of methylmyristate alpha-sulfonic acid.

(F) 75 of (y) ethoxylated palmityl alcohol (10 mols of ethylene oxide) sulfate neutralized with octadecyl propylene diamine and 25% of (x) sulfated dinonylphenol (ethoxylated with 10 mols of ethylene oxide) neutralized with octadecyl propylene diamine.

(y) Sulfated lauryl alcohol (ethoxylated with 6 mols of ethylene oxide) neturalized with octyl amine.

The preparation of component (a) is done by neutralization as follows:

(I) One gram mol of methylmyristate alpha-sulfonic acid (in a paste-form with an equal weight of water) is mixed with one gram mol of ethylenediamine, and the reaction proceeds readily with stirring and gentle warming (to about 50 C.) to obtain the basic salt of ethylenediamine and methylmyristate alpha-sulfonic acid.

(II) A procedure is carried out that is the same as that described in the previous paragraph (I) except that the polyamine used is diethylene tn'amine, propylene diamine, butylene diamine, penta-ethylene hexamine, stearyl propylene diamine, hexadecyl propylene diamine, tetradecyl ethylene diamine, stearoyl imidazoline, myristoyl ethanol imidazoline, palmityl propanol imidazoline and, in each case, the corresponding basic salt is obtained.

(III) A procedure is carried out that is the same as the previous paragraph (II) except that the ester-acid used is ethyl palmitate alpha-sulfonic acid, isopropyl stearate alpha-sulfonic acid, sec.-butyl myristate alpha-sulfonic acid, iso-amyl laurate alpha-sulfonic acid and n-hexyl decanoate alpha-sulfonic acid; and, in each case, the corresponding basic salt is obtained. But if 2 gram mols of each of such ester-acids is used to react with the aforesaid polyamines in the same procedure, the resulting salts are substantially neutralized (although actually still quite alkaline reacting) salts in the case of ethylene diamine, propylene diamine, butylene diamine, hexadecyl propylene diamine, stearyl propylene diamine, and the like diamines. With polyamines containing more than two amino groups, however, the resulting reaction product is still a basic salt. Reaction of one mol of the ester-acid for each amino group in a polyamine results in the neutralized salt (e.g. 3 mols of methyl myristate alpha-sulfonic acid and one mol of diethylene triamine).

(IV) The basic and neutralized salts of polyvalent metals are prepared in substantially the same manner. Thus, one gram mol of methylmyristate alpha-sulfonic acid (in paste form with an equal weight of water) is mixed with one gram mol of calcium hydroxide and the reaction proceeds readily with stirring and gentle warming (to about 50 C.) to obtain the basic calcium salt of methylmyristate alpha-sulfonic acid. Using the same procedure with twice as much of the methylmyristate alphasulfonic acid, one obtains a neutralized salt. Using barium hydroxide, one obtains the basic barium salt and the neutralized barium salt, respectively, using the two procedures just set forth. Likewise, the basic and neutralized salts of other polyvalent metals such as magnesium, zinc, strontium, copper (cupric), tin (stannous), aluminum, manganese, cobalt, nickel, etc. are obtained in each case using either the base of the metal or a soluble salt thereof such as the chloride which permits the formation of the relatively less soluble sulfonic acid of the particular metal. These salts of metals other than the alkali metals and the alkaline earth metals are functional emulsifiers (and may thus be used in dry cleaning compositions or the like), but they are more useful in other fields, for such purposes as paint dryers, lubricating oil additives, etc.

We claim as our invention:

1. A dry cleaning composition consisting essentially of a mixture of water emulsified in a volatile organic dry cleaning solvent, said mixture being in amounts sufiicient for dry cleaning operations and, as a dry cleaning assistant in a small detersive amount ranging from about 0.25% to 5% by weight a detergent component consisting essentially of (y) detergent having the formula:

wherein AO- is the residue of a fatty alcohol; A-OH wherein A has from six to twenty-two carbon atoms, In is an integer from 1 to 50 and M" is selected from the group consisting of alkali metals, alkaline earth metals, ammonium (C -C alkylol) ammonium (C -C alkoxy),,- (C -C alkylol) ammonium wherein n is an integer from 1 to 50, poly(C -C alkylene) amines, primary, secondary, tertiary and quaternary alkyl ammonium wherein the alkyl groups contain a total of one to twenty carbon atoms, C to C aliphatic (C -C alkylol) amines, C

to C alkyl NH(CI-I amines wherein m is an integer from 1 to 4 and imidazolines having the formula:

II I n -o on,

wherein Y is selected from the class consisting of C-O and R is a C to C fatty acid residue; X is selected from the group consisting of C to C hydrocarbon, glyceryl, C -C alkyl ether of glycerol, (C -C alkoxy),,R' where in n is an integer from 1 to 50 and R is selected from the group consisting of H and C C alkyl groups; and M is selected from the group consisting of H and C -C alkyl groups; and M is selected from the group consisting of alkali metals, alkaline earth metals, ammonium, (C C alkylol) ammonium, (C -C alkoxy) (C C alkylol) ammonium wherein n is an integer from 1 to 50, poly- (C -C alkylene) amines, and, primary, secondary tertiary and quarternary alkyl ammonium wherein the alkyl groups contain a total of two to twenty carbon atoms, C to C aliphatic (C -C alkylol) amines, C to C alkyl NH(CH amines wherein m is an integer from 1 to 4imidazo1ines having the formula:

wherein R" is a C to C fatty acid residue and R is selected from the group consisting of C to C alkyl, C to C alkylol and H; the minimum total number of carbon atoms in any C to C chain in X plus any C to C chain in M, plus the carbon chain in R being twelve and (x) detergent having the formula:

RIM U I II R I! wherein R' is a C to C fatty acid residue and R" is selected from the group consisting of C to C alkyl, C to C alkylol and H, the weight ratio of (a) and (x) ranging from 20:1 to 1:20, and the weight ratio of (y) to (a) plus (x) being from 34:66 to 100:1, and the amount of (y) being greater than the amount of (x) and greater than the amount of (a).

2. A method of dry cleaning textile fabrics which com prises rinsing the fabrics in a dry cleaning composition consisting essentially of a mixture of water emulsified in a volatile organic dry cleaning solvent, said mixture being in amounts sufiicient for dry cleaning operations and, as a dry cleaning assistant in small detersive amounts ranging from about 0.25% to 5% by weight a detergent component consisting essentially of (y) detergent having the formula:

wherein AO is the residue of a fatty alcohol: AOH wherein A has from six to twenty-two carbon atoms, m is an integer from 1 to 50 and M is selected from the group consisting of alkali metals, alkaline earth metals, ammonium, (C C alkylol) ammonium ammonium wherein n is an integer from 1 to 50, poly- C CA, alkylene) amines, primary, secondary, tertiary and quaternary alkyl ammonium wheerin the alkyl groups contain a total of one to twenty carbon atoms, C to C aliphatic (C -C alkylol) amines, C to C alkyl NH(CH amines wherein m is an integer from 1 to 4 imidazolines having the formula:

NOH2

wherein R is a C to C fatty acid residue and R" is selected from the group consisting of C to C alkyl, C, to C alkylol and H, (a) detergent having the formula:

RCHYX som wherein Y is selected from the class consisting of and C-NH- R is a C to C fatty acid residue, X is selected from the group consisting of C to C hydrocarbon, glyceryl, C C alkyl ether of glycerol, (C -C alkoxy) R' wherein n is an integer from 1 to 50 and R is selected from the group consisting of H and C -C alkyl groups; and M is selected from the group consisting of alkali metals, alkaline earth metals, ammonium, (C -C alkylol) ammonium, (C -C alkoxy) (C -C alkylol) ammonium wherein n is an integer from 1 to 50, poly(C -C alkylene) amines, and, primary, secondary, tertiary and quaternary alkyl ammonium wherein the alkyl groups contain a total of two to twenty carbon atoms, C to C aliphatic (C C, alkylol) amines, C to C alkyl NH(CH amines wherein m is an integer from 1 to 4 and imidazolines having the formula:

wherein R' is a C to C fatty acid residue and R' is selected from the group consisting of C to C alkyl, C to C alkylol and H; the minimum total number of carbon atoms in any C to C chain in X plus any C to C chain in M, plus the carbon chain in R being twelve and (x) detergent having the formula:

wherein R" is a C to C alkyl group, 1' is an integer from one to two, n is an integer from one to fifty, D is selected from the group consisting of O and S: and M is selected 13 from amine bases consisting of C to C aliphatic mono-, di-, tri-, and quaternary amines, C to C aliphatic (C C alkylol) amines, C to C alkyl .NH-(CH amines wherein m is an integer from 1 to 4 and imidazolines having the formula:

I]\IOH2 RIII J 5H2 (y) being greater than the amount of (x) and greater than the amount of (a).

References Cited UNITED STATES PATENTS 3,274,117 "5/1963 Stein et a1. 2521'6 1 2,941,952 6/1960 Lewis et al. 252-471 2,326,772 8/1943 Flett 252-161 3,247,121 4/ 1966 Hendricks 252117 3,128,294 4/ 1964 Stirton et a1. 252-16 1 XR LEON D. ROSDOL, Primary Examiner.

B. BETIS, Assistant Examiner.

U.S. Cl. X.R. 252152, 161, 171 

